CN116987474A - 一种生物基耐老化聚氨酯胶黏剂 - Google Patents
一种生物基耐老化聚氨酯胶黏剂 Download PDFInfo
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Abstract
本发明提供了生物基耐老化聚氨酯胶黏剂及其制备方法。本发明是通过优化多元醇和固化剂的原料组合，获得以腰果壳油聚醚多元醇、山梨醇和木糖醇组合的生物基多元醇为原料，以对苯二酚二羟乙基醚和3,5‑二甲硫基甲苯二胺复配为固化剂进一步通过丙酮法合成生物基耐老化聚氨酯胶黏剂。经证实，本发明的生物基耐老化聚氨酯胶黏剂能保持较好的抗冲击强度、拉伸强度、断裂伸长率以及耐老化性能，满足工业化生产的需求和应用。
Description
技术领域
本发明涉及高分子技术领域，特别涉及一种生物基耐老化聚氨酯胶黏剂。
背景技术
聚氨酯是由大分子二醇作为软段，多异氰酸酯、低分子量二元醇或二元胺为硬段聚合成主链上含有氨基甲酸酯的重复结构单元的高分子聚合物。其具备耐磨、抗撕裂、抗挠曲性好等优点，是高分子材料中唯一在塑料、橡胶、纤维、涂料、胶粘剂和功能高分子等领域均有应用价值的有机合成材料。
但聚氨酯传统的原料来源于石油，原料不可再生，具有剧毒，同时，废聚氨酯降解困难，污染环境。生物基聚氨酯材料具有很好的生物可降解性，原料来源广泛，对环境负荷小。生物基聚氨酯材料的合成主要是通过共混或共聚的方法引入生物降解成分或基团，如聚乳酸/聚丙交酯(PLA)、聚羟基乙酸(PGA)等。
但是，由于生物基材料与聚氨酯结合难、耐久耐用性差、生物基基布强度不够等原因，生物基聚氨酯胶合成还处于探索阶段，开发一种具备良好机械性能和耐久性生物基耐老化聚氨酯胶黏剂合成是具有重要意义。
发明内容
针对现有技术所存在的技术问题，本发明提供了一种生物基耐老化聚氨酯胶黏剂。本发明的生物基耐老化聚氨酯胶黏剂能保持较好的抗冲击强度、拉伸强度、断裂伸长率以及耐老化性能，满足工业化生产的需求和应用。
具体而言，本发明首先提供了一种生物基耐老化聚氨酯胶黏剂，其特征在于，所述生物基耐老化聚氨酯胶黏剂的配方包括生物基多元醇和固化剂组成，其中所述生物基多元醇是选自腰果壳油聚醚多元醇、蓖麻油多元醇、山梨醇、木糖醇、甘露醇、麦芽糖醇、甘油和乙二醇的一种或多种；所述固化剂是选自二醇类固化剂或二胺类固化剂。
优选地，所述生物基多元醇选自腰果壳油聚醚多元醇、山梨醇和木糖醇。
优选地，所述腰果壳油聚醚多元醇、山梨醇和木糖醇的用量比为1:1:1。
优选地，所述二醇类固化剂是选自对苯二酚二羟乙基醚、间苯二酚双羟乙基醚、对羟乙基双酚A中的一种或多种；所述二胺类固化剂是选自3,5-二甲硫基甲苯二胺、3,3'-二氯-4,-4'二苯基甲烷二胺、3,5二乙基甲苯二胺的一种或多种。
优选地，所述固化剂是选自对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺。
优选地，所述对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺的用量比为1:1。
优选地，所述生物基多元醇和固化剂的用量比为1:3。
本发明另一个目的在于提供了一种生物基耐老化聚氨酯胶黏剂的制备方法，其包括如下步骤：
1)在干燥氮气保护下，将多元醇加入反应容器中，于120±10℃下减压除水2-3h，接着将体系温度降低至40-70℃；
2)向所述反应容器中加入异佛尔酮二异氰酸酯、固化剂和催化剂，混合均匀后，使用稀释剂调节混合液的粘度，于40-70℃反应6-8h；
3)待步骤S2反应结束后加入扩链剂进行交联反应，搅拌，使所述聚合物乳化形成乳液；
4)蒸馏回收所述乳液中的稀释剂，即得到所述生物基耐老化聚氨酯胶黏剂材料。
其中，步骤1)中的多元醇是选自腰果壳油聚醚多元醇、蓖麻油多元醇、山梨醇、木糖醇、甘露醇、麦芽糖醇、甘油和乙二醇的一种或多种；
优选地，步骤1)中的多元醇是选自腰果壳油聚醚多元醇、山梨醇和木糖醇中的一种或多种；
进一步优选地，所述多元醇是选自腰果壳油聚醚多元醇、山梨醇和木糖醇；
进一步优选地，所述多元醇中腰果壳油聚醚多元醇、山梨醇和木糖醇的质量比为1:1:1；
其中，步骤2)中的固化剂是选自二醇类固化剂或二胺类固化剂；
优选地，所述二醇类固化剂是选自对苯二酚二羟乙基醚、间苯二酚双羟乙基醚、对羟乙基双酚A中的一种或多种；
优选地，所述二胺类固化剂是选自3,5-二甲硫基甲苯二胺、3,3'-二氯-4,-4'二苯基甲烷二胺、3,5二乙基甲苯二胺的一种或多种；
进一步优选地，所述固化剂是选自对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺；
进一步优选地，，所述固化剂中对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺的质量比为1:1；
其中，步骤2)中的催化剂是选自辛酸亚锡、二月桂酸二丁基锡、有机铋催化剂中的一种或多种；
优选地，所述催化剂是辛酸亚锡；
其中，步骤2)中的稀释剂是选自丙酮；
其中，步骤3)中的扩链剂是选自三羟甲基丙烷、甘油、二乙醇胺、三乙醇胺、乙醇胺中的一种或多种；
优选地，所述扩链剂是三羟甲基丙烷；
本发明的优点在于：1)本发明的一种生物基耐老化聚氨酯胶黏剂具备很高的抗冲击强度，最高可达到38.453KJ/m2，拉伸强度最高可达到99.65Mpa，断裂伸长率最高可保持在396.55％。同时，经过100℃热空气老化1000h后，本发明的生物基耐老化聚氨酯胶黏剂仍然保持较高的冲击强度、拉伸强度和断裂伸长率。
2)本发明的一种生物基耐老化聚氨酯胶黏剂中，以腰果壳油聚醚多元醇、山梨醇和木糖醇组合的生物基多元醇存在协同作用，三者复配的抗冲击耐老化的效果明显是优于单个多元醇和两个多元醇的组合效果。此外，进一步优化固化剂的配方可知，采用对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺复配的固化剂会明显提升生物基聚氨酯产品机械性能，尤其是对于拉伸强度的改善，并且经过100℃热空气老化1000h后，生物基聚氨酯产品仍旧能保持较好的抗冲击强度、拉伸强度和断裂伸长率，满足工业化生产的需求和应用。
具体实施方式
下面结合具体实施例对本发明作进一步的详细说明，以使本领域的技术人员更加清楚地理解本发明。
以下各实施例，仅用于说明本发明，并不用来限制本发明的范围。基于本发明中的具体实施例，本领域普通技术人员在没有做出创造性劳动的情况下，所获得的其他所有实施例，都属于本发明的保护范围。
在本发明实施例中，若无特殊说明，所有原料组分均为本领域技术人员熟知的市售产品；在本发明实施例中，若未具体指明，所用的技术手段均为本领域技术人员所熟知的常规手段。
实施例1-5生物基耐老化聚氨酯胶黏剂及其制备
一种生物基耐老化聚氨酯胶黏剂的制备方法，其包括如下步骤：
1)在干燥氮气保护下，将多元醇加入反应容器中，于120±10℃下减压除水2-3h，接着将体系温度降低至40-70℃；
2)向所述反应容器中加入异佛尔酮二异氰酸酯、固化剂和催化剂，混合均匀后，使用稀释剂调节混合液的粘度，于40-70℃反应6-8h；
3)待步骤S2反应结束后加入扩链剂进行交联反应，搅拌，使所述聚合物乳化形成乳液；
4)蒸馏回收所述乳液中的稀释剂，即得到所述生物基耐老化聚氨酯胶黏剂材料。
表1.实施例1-5的生物基耐老化聚氨酯胶黏剂的合成配方
将实施例1-5中制备的一种生物基耐老化聚氨酯胶黏剂与固化剂氨基乙基哌嗪按照质量比4:1的比例混合均匀后加入测量拉伸和冲击的模具中，在30℃下预固化5h，而后放置烘箱于85℃下后固化12h，取出冷却后进行低温抗冲击性能和耐化学性能测试以及耐老化性能，结果如下表2所示。
表2.物理性能表征
从表2中可以看出，由本发明的一种生物基耐老化聚氨酯胶黏剂具备很高的抗冲击强度，最高可达到38.453KJ/m2，拉伸强度最高可达到99.65Mpa，断裂伸长率最高可保持在396.55％。同时，经过100℃热空气老化1000h后，本发明的生物基耐老化聚氨酯胶黏剂仍然保持较高的冲击强度、拉伸强度和断裂伸长率。
并且，通过实施例3和实施例1-2的对比可以发现，以腰果壳油聚醚多元醇、山梨醇和木糖醇组合的生物基多元醇存在协同作用，三者复配的抗冲击耐老化的效果明显是优于单个多元醇和两个多元醇的组合效果。此外，在实施例3的基础上进一步优化固化剂的配方可知，采用对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺复配的固化剂会明显提升生物基聚氨酯产品机械性能，尤其是对于拉伸强度的改善，并且经过100℃热空气老化1000h后，生物基耐老化聚氨酯胶黏剂产品仍旧能保持较好的抗冲击强度、拉伸强度和断裂伸长率，满足工业化生产的需求和应用。
在此有必要指出的是，以上实施例仅限于对本发明的技术方案做进一步的阐述和说明，并不是对本发明的技术方案的进一步的限制，本发明的方法仅为较佳的实施方案，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种生物基耐老化聚氨酯胶黏剂，其特征在于，所述生物基耐老化聚氨酯胶黏剂的配方包括生物基多元醇和固化剂组成，其中所述生物基多元醇是选自腰果壳油聚醚多元醇、蓖麻油多元醇、山梨醇、木糖醇、甘露醇、麦芽糖醇、甘油和乙二醇的一种或多种；所述固化剂是选自二醇类固化剂或二胺类固化剂。
2.如权利要求1所述的生物基耐老化聚氨酯胶黏剂，其特征在于，所述生物基多元醇选自腰果壳油聚醚多元醇、山梨醇和木糖醇。
3.如权利要求2所述的生物基耐老化聚氨酯胶黏剂，其特征在于，所述腰果壳油聚醚多元醇、山梨醇和木糖醇的用量比为1:1:1。
4.如权利要求1所述的生物基耐老化聚氨酯胶黏剂，其特征在于，所述二醇类固化剂是选自对苯二酚二羟乙基醚、间苯二酚双羟乙基醚、对羟乙基双酚A中的一种或多种；所述二胺类固化剂是选自3,5-二甲硫基甲苯二胺、3,3'-二氯-4,-4'二苯基甲烷二胺、3,5二乙基甲苯二胺的一种或多种。
5.如权利要求4所述的生物基耐老化聚氨酯胶黏剂，其特征在于，所述固化剂是选自对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺。
6.如权利要求5所述的生物基耐老化聚氨酯胶黏剂，其特征在于，所述对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺的用量比为1:1。
7.如权利要求1-6任一项所述的生物基耐老化聚氨酯胶黏剂，其特征在于，所述生物基多元醇和固化剂的用量比为1:3。
8.权利要求1-7任一项所述的生物基耐老化聚氨酯胶黏剂的制备方法，其特征在于，所述包括如下步骤：
1)在干燥氮气保护下，将多元醇加入反应容器中，于120±10℃下减压除水2-3h，接着将体系温度降低至40-70℃；
2)向所述反应容器中加入异佛尔酮二异氰酸酯、固化剂和催化剂，混合均匀后，使用稀释剂调节混合液的粘度，于40-70℃反应6-8h；
3)待步骤S2反应结束后加入扩链剂进行交联反应，搅拌，使所述聚合物乳化形成乳液；
4)蒸馏回收所述乳液中的稀释剂，即得到所述生物基耐老化聚氨酯胶黏剂材料。
9.如权利要求8所述的制备方法，其特征在于，步骤2)中的催化剂是选自辛酸亚锡、二月桂酸二丁基锡、有机铋催化剂中的一种或多种，步骤2)中的稀释剂是选自丙酮。
10.如权利要求8所述的制备方法，其特征在于，步骤3)中的扩链剂是选自三羟甲基丙烷、甘油、二乙醇胺、三乙醇胺、乙醇胺中的一种或多种。
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